METALLOPORPHYRINS, SPIN AND FULLERENES

描述：(改编自申请者的摘要)本项目探索 卟啉和富勒烯的基本化学性质 发现新的化学物质，为分子水平的理解奠定基础 生物和医学。它专注于铁的自旋态，弱相互作用 金属与配体之间、超分子化学与C60的新反应性。 具体目标包括寻找‘失踪’的纯S=3/2自旋态 铁(III)卟啉及其配位场反转的研究 新的“磁化学系列”中OH-和H2O的强度顺序与 熟悉的光谱化学系列。一种超结构的金属卟啉，这给了 上升到第一个不溶性的烷烃络合物，将用于研究 氙气的潜在络合物。富勒烯阳离子化学将被探索到 开发富勒离子作为合成子，用于清洁的C60单官能化。 富勒离子的弱而不稳定的二聚化假说，例如形成 [(C60)2]-和[(C60)2]2-，将通过构造 单体和二聚富勒烯部分的超分子陷阱。自性 组装金属卟啉立方体和盒子的设计是为了封装 C60、C70和(C60)2及其各自的富勒烷阴离子。阳离子C60 正在准备Ru和Os的络合物用于生物测试，如 抗病毒和抗癌药物。泛函的结构表征 将继续探索细胞色素氧化酶的血红素A3/幼崽活性部位的模型。 所有这些研究的重点都将放在确定的 用X射线结晶学对分析纯材料的表征 电化学方法和各种光谱方法(核磁共振、红外光谱、 电子光谱包括近红外、穆斯堡尔、共振拉曼等)。一个 对这一基本的生物无机化学的理解必须是医学的基础 金属蛋白紊乱(地中海贫血、镰刀状贫血)的治疗方法 细胞性贫血等)。富勒烯具有潜在的应用前景，如 放射性药物、抗病毒药物、抗癌药物、光动力疗法 代理和作为核磁共振的代理。

DESCRIPTION: (adapted from applicant's abstract) This project explores the fundamental chemical properties of porphyrins and fullerenes with the goal of discovering new chemistry that underpins the molecular level understanding of biology and medicine. It focuses on the spin states of iron, weak interactions between metals and ligands, supramolecular chemistry and new reactivity of C60. The specific aims include a search for the 'missing' pure S = 3/2 spin state of iron(III) porphyrins and an investigation into the reversal of ligand field strength order of OH- and H2O in the new "Magnetochemical Series" versus the familiar Spectrochemical Series. A superstructured metalloporphyrin, that gave rise to the first insoluble complex of an alkane, will be used to investigate potential complexes of xenon. Fullerene cation chemistry will be explored to develop fullerenium ions as synthons for clean monofunctionalization of C60. The weak, labile dimerization hypothesis for fulleride ions, e.g. the formation of [(C60)2]- and [(C60)2]2-, will be tested by the construction of supramolecular traps for monomeric and dimeric fullerene moieties. Self assembling metalloporphyrin cubes and boxes have been designed to encapsulate C60, C70 and (C60)2 and their respective fulleride anions. Cationic C60 complexes of ruthenium and osmium are being prepared for biological testing as anti-viral and anti-cancer drugs. The structural characterization of functional models for the heme a3/CuB active site of cytochrome oxidase will be pursued. Emphasis in all of these studies will be placed on the definitive characterization of analytically pure materials by X-ray crystallography, electrochemical methods and a variety of spectroscopic methods (NMR, IR, electronic spectroscopy including NIR, Mossbauer, resonance Raman, etc). An understanding of this fundamental bioinorganic chemistry must underlie medical approaches to the therapy of metalloprotein disorders (thalassemias, sickle cell anemia, etc). Fullerenes have potential applications as radiopharmaceuticals, anti-virals, anti-cancer drugs, photodynamic therapy agents and as MRI agents.